New polymerizable vinyl ether quaternary ammonium compounds



2,897,200. Patented July 28, 1959 NEW POLYMERIZABLE VINYL ETHER QUATER- NARY AMMONIUM COMPOUNDS Arthur Maeder, Base], and Otto Albrecht, Neuewelt,

near Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland No Drawing. Application October 25, 1954 Serial No. 464,600

Claims priority, application Switzerland October 30, 1953 4 Claims. (Cl. 260-2473) This invention is based on the observation that vinyl ethers which contain at least one quaternary ammonium group which is not bound to a hetero-atom through a methylene bridge, are valuable compounds for the manufacture of polymers and copolymers. The statement that the quaternary ammonium group must not be bound to a hetero-atom through a methylene bridge means that at least two carbon atoms must lie between the ammonium group and the nearest hetero-atom. As starting materials for making the quaternary ammonium compounds there are suitable vinyl ethers, which contain at least one tertiary amino group which is not bound to a hetero-atom by a methylene bridge. Such compounds are known or can be made by methods in themselves known. There may be used compounds which contain aliphatic, aromatic or hetero-cyclic residues. There also come into consideration compounds which contain a component capable of undergoing hardening. This compound can be obtained by the action of a suitable basic vinyl ether on a formaldehyde condensation product of an amino-triazine compound or a urea compound. Among the compounds suitable for conversion into quaternary ammonium compounds the following examples may be mentioned:

Advantageously, those compounds are used which contain only one tertiary amino group and which have only aliphatic residues or aliphatic and heterocyclic residues in the molecule, or those, in so far as they contain aromatic .residues, which possess only one such aromatic residue,

namely a six-membered ring, that is to say a benzene residue which can be substituted, if desired.

The quaternation of the vinyl ethers may be carried out by methods in themselves known by the action of compounds which are capable of converting a tertiary amino group into a quaternary ammonium group, and there come into consideration more especially the usual alkylating or aralkylating agents, such as dimethylsulfaite, methyliodide, benzylchloride and nuclear substitution products thereof. Especially advantageous is the use of such quaternating agents as contain a reactive atom group ing. Under the expression reactive atom grouping are to be understood, for example, epoxy groups, movable halogen atoms, acetal groups and more especially hydrogen atoms bound to hetero-atoms. There come into consideration hydroxyl groups, amide groups, N-methylol-amide groups; especially advantageous quaternating agents are epichlorhydrin and chloracetamide. The use of quaternating agents with reactive atom groupings has the advantage that compounds are formed which, in addition to being polymerizable, are capable of further reactions, which property polymerization and copolymerization products prepared from monomeric compounds usually also possess. Such monomeric or polymeric compounds can, for example, be used for cross-linking reactions. If salts of vinyl ethers are used with a tertiary amino group, alkylene oxides, such as ethylene oxide may be used as quaternating agents.

The new quaternary ammonium compounds are watersoluble in the monomeric condition, provided that they have been derived from the usual inorganic or organic acids. They may be polymerized alone or jointly With other polymerizable compounds.

The polymerization may be carried out in bulk, in solution or in emulsion, the usual conditions employed in polymerization techniques being used. Thus, it is of advantage to use a polymerization catalyst. The usual compounds which catalyse polymerization may be added. For the polymerization of the vinyl ethers alone there may be used the usual Friedel-Crafts catalysts such as aluminum chloride, boron fluoride or stannic chloride. For the purpose of copolymerization there may be used catalysts, such as organic or inorganic peroxides, or per salts, for example, peracetic acid, acetyl peroxide, benzoyl peroxide, benzoyl-acetylperoxide, lauryl peroxide,

. cumenehydroperoxide, tertiary butylhydro-peroxide, para-,

methanehydroperoxide, hydrogen peroxide, percarbonates, persulfates or perborates. The proportions in which they are added depends, as is known, on the course of reaction desired and on the properties desired in the polymer. If desired, a plurality of agents catalyzing the polymerization may be used. The. action of the polymerization catalysts may be enhanced by the simultaneous action of heat and/ or actinic rays. Alternatively, the polymerization may be brought about by heat and/or actinic rays without the addition of a catalytic compound. In order to modify the speed of the polymerization and the molecular Weight of the polymer, so-called regulators such, for example, as mercaptans, terpenes or the like may be added.

It is also of advantage to carry out the polymerization in the absence of air or oxygen and in the presence of an inert gas, such as nitrogen or carbondioxide. In addition to the aforesaid catalysts and regulators, so-called activators may be used. Such activators are, for example, inorganic oxidizable oxygen-containing sulfur compounds such as sulfur dioxide, sodium bisulfite, sodium sulfite, ammonium bisulfite, sodiumhydrosulfite or sodium thiosulfate. By using simultaneously an activator and a polymerization catalyst yielding oxygen a so-called Redox systern is formed, which favorably influences the polymerization process. As activators there may also be used watersoluble aliphatic tertiary amines such as, triethanolamine, diethyl-ethanolamine. The action of the polymerization catalyst can be accelerated by the addition of a heavy metal compound, which is capable of existing in more.

than one valency stage and is present in a reduced condition, or by addition of a complex cyanide of iron, cobalt, molybdenum, mercury, zinc, copper or silver or a mixture of such complexes. When the. polymerization is carried out in emulsion, the monomeric compounds are advantageously emulsified with the aid of emulsifying. agents, as emulsifying agents there come into consideration those of the. cation-active or non-ionogenic character. Among the cation-active emulsifying agents. there may be used, for example, compounds of higher fatty amines. with acetic acid, hydrochloric acid or sulfuric acid, such as octadeeylamine acetate, (dodecyl)-diethyl-cyclohexylaminesulfate and. also. salts of diethyl amino-ether esters and fatty acids or salts of the type of oleylamidoethyl-diethylamino acetate C H CONHC H NH C H .OCO .CH There are also suitable quaternary ammonium compounds, such as cetyl-dimethyl-benzylammonium-chloride, cetyl-trimethylammonium bromide, para-(trirnethylammonium) -benzoic acid acetyl ester-methosulfate, cetylpyridinium-metho sulfate, octadecyltrimethyl-ammonium bromide or the quaternary compound obtained from diethylsulfate and triethanolamine-tristearate.

Among the non-ionogenic emulsifying agents there may be mentioned polyglycol ethers and fatty acids, fatty amines or fatty alcohols of high molecular weight such as cetyl alcohol, oleyl alcohol or octadecyl alcohol, for example, the reaction product of 15-30 mols of ethyleneoxideand one mol of the fatty alcohol. There may also be used emulsifying agents having a wetting action suchas octylphenolpolyglycol ethers, and also lauryl alcohol polyglycol ethers or polyhydric alcohols partially esten'fied with higher fatty acids, for example, glycerine monolaurate, or sorbitol monolaurate. There may also be used mixtures of such emulsifying agents, or mixtures of such emulsifying agents with protective colloids such as polyvinyl alcohols, partially hydrolyzed polyvinylesters, and also starches or starch derivatives, for example, dextrin; and furthermore cellulose ethers, polyethylene oxides, and generally water-soluble polymers or copolymers which contain free hydroxyl, amino or carboxylic acid amide groups. Finally, such a protective colloid may be used. alone.

' Whenthe polymerization iscarried' out in-solution there maybe used a solvent in which only the monomeric compounds are soluble and in which the polymers. are. in-

soluble. However, there may also be used solvents in Which the polymers are also soluble. Suitable solvents are, for example water and organic solvents, such as methylene chloride or dichloro-ethane.

The polymerization may be carried out at ordinary temperatures, but more advantageously at a raised temperature. Suitable temperatures are, for example, 40-95 C. and especially 55-90 C. In some polymerizations there is often a considerable amount of heat liberated, so that it is necessary to use suitable cooling devices in order to maintain the desired polymerization temperature. This is necessary when a large quantity of material is to be polymerized in one batch. In order to utilize the heat liberated and to control the polymerization temperature more easily, it has been found advantageous in the case of emulsion polymerizations, for example, to place in a polynnerization apparatus a small portion of the total amount of an emulsion to be treated, and to initiate the polymerization in this portion. When this portion of the emulsion reaches a certain temperature, for example, 6070 C. the remaining cold' emulsion is run in in such manner that the temperature is kept constant. Towards the end of the polymerization it is often necessary to supply heat externally.

Depending on the conditions of polymerization and on the starting materials used the polymeric compounds are obtained in the form of viscous solutions, granulates or in the form of emulsions. The products resulting from the polymerization may be used directly without. further working up. It is often preferable, however, to work them up in a suitable manner before hand. There may be added, for example, modifying substances such as softening agents, for example, dibutylphthalate or dioctylphthalate or sebacic' acid esters, or organic or inor ganic pigments or filling materials. The copolymeri'zatio'n of the monomeric compounds with other polymerizable compounds may also be carried out in the presence of substrata. Textile material is advantageously impregnated with a solution or emulsion of the monomers and then the copolymerization is brought about with the addition of apolymerizat-ion catalyst by heating the material.

As stated above, the products of the invention may be polymerized with other unsaturated polymerizabl'e compounds. As such compounds there are especially suitable those which contain the atomic grouping OH =C such as vinyl, esters. of organic acids, for example, vinyl acetate, vinyl' formate, vinyl butyrate or vinyl benzoate and also vinyl alkyl lietones, vinyl halides, such as vinyl chloride or vinyl fluoride, vinylidene chloride or vinyl aryl compounds such as styrene and substituted styrenes, and also compounds of the acrylic acid series, such as esters of acrylic acid with. alcohols. or phenols, for example, ethylacrylate, butylacrylate, dodecylacrylate, acrylonitrile or acrylic acid amide and its derivatives substituted at the amide-nitrogen atom, and also analogous derivatives of methylacrylic acid, ot-chloracrylic acid. There may also be used polymerizable olefines such as isobutylene, butadiene or Z-chlor-butad'iene, or heterocyclic compounds containing. at least one vinylgroup such as vinyl pyridine. Advantageously there are used derivatives of acrylic acid. Binary, ternary or more complex copolymerscan be made, of which the properties can be regulated by suitable choice of starting materials, the relative proportions of the individual components and the conditions of polymerization.

The polymeric products obtainable by the process of the. invention are suitable for a very wide variety of purposes. They are generally applicable for all purposes involving the use offpolymeriz-ation. resins or'pollymerization' andcondensation resins; They can be used for the manufacture of moulding masses and moulded bodies, fihns, fibers, adhesives or lacquers. Certain of the copolymers possess a: rubber-like character, and are suitable as rubber substituted which are resistant to benzene and benzine. The products, provided that they have been made from suitable starting materials, can be used, inter alia, as assistants in the textile, leather and paper industries. They can be used for the production of impregnations and coatings, for example, textiles may be rendered water-repellent by means of suitably substituted compounds. Other polymers are suitable for animalizing cellulose-containing textile materials, or as after-treating agents for improving the fastness to washing and water of dyeings or prints of water-soluble directdyeing dyestufis which owe their solubility in water to the presence of sulfonic acid or carboxylic acid groups. Such an after-treatment may be coupled with an after-treatment with a copper salt. The new products may also be used for dyeing, printing and dressing natural or artificial fibers with pigments or'for producing matt effects on polyamide fibers.

In general the products of the invention yield dressings which withstand wear well in use.

The following examples illustrate the invention, the parts being by weight:

Example 1 A mixture of 14.3 parts of fi-diethylaminoethylvinyl ether and 9.35 parts of chloracetamide are heated in a boiling water bath for 6 hours while stirring. After cooling the mixture, 0.3 part of the unchanged vinyl ether is poured olf, and the viscous resinous reaction mass is dissolved in 23 parts of water. In this manner there is obtained a solution of about 50 percent strength of the quaternary compound of the formula CHFCH-OCHg-CHg-N Ol- C1120 ONHz which solution can be used for polymerizations without further purification.

Example 2 which solution can be used for polymerizations without further purification.

Example 3 .21 parts of styrene and 6 parts of n-butyl acrylate are emulsified, while vigorously stirring mechanically or shaking, in a mixture of 6 parts of the solution of about 50 percent strength of the quaternary compound described in Example 1, 2 parts of trioxyethyl-lauryl-ammonium acetate, 0.1 part of isooctanol and 67 parts of distilled water. The emulsion is polymerized with the addition of 2 parts of a potassium persulfate solution of 10 percent strength, while stirring, at 70-80 C. for 5 hours. After filtering 01f a very small amount of coarse constituents, there is obtained a stable thinly liquid finely divided dispersion having a polymer content of 28 percent, which is suitable for dressing purposes, especially for the production of a matt efiect on a fabric of finely fibrous polyamide.

.6 Example 4 The procedure is the same as in Example 3, except that the quaternary ammonium compound used therein is replaced by the same quantity of the quaternary compound prepared as described in Example 2. There is likewise obtained a thinly liquid stable finely divided emulsion, which has a dry content of 28 percent and is suitable for dressing purposes.

Example 5 The procedure is the same as that described in Example 4, except that instead of 67 parts only 31 parts of distilled water are used for the emulsification. In this manner there is obtained a stable thinly liquid finely divided emulsion having a dry content of 46 percent.

An emulsion polymerization of styrene and n-butylacrylate carried out in a precisely analogous manner, but without the addition of a polymerizable quaternary ammonium compound, yields no emulsion and large masses of the copolymer separate out.

Example 6 CH2CE CHFCH-O-CHa-CHz-N O GHQ-C is obtained, which solution can be used for copolymerizations without further purification.

Example 7 25 .22 parts of dimethyl sulfate /s mol) are added dropwise at room temperature while stirring to a solution of 31.44 parts of (fl-morpholino-ethyl)-vinyl ether (Vs mol) in 50 parts of methylene chloride in the course of half an hour. The temperature rises owing to the reaction heat, and the solvent finally boils weakly under reflux. The whole is stirred for a further /2 hour until the reaction is completed, and a clear solution of 54 percent strength of the quaternary ammonium compound of the formula in methylene chloride is obtained, which solution is suitable for polymerizations.

In an analogous manner (,B-morpholinoethyl)-vinyl ether can be converted also with para-toluene sulfonic acid methyl ester into the corresponding quaternary ammonium compound when equivalent quantities of these compounds dissolved in methylene chloride are allowed to react together.

" Example 8 12.61 parts A mol) of dimethyl sulfate are added dropwise in the course of 10 minutes while stirring to a 04119 [GE -CH-O-CH CHz-N-CH;:l-OSO OH{ AHB is suitable for polymerizations without further purificatron.

Example9 12.61 parts mol) of dimethyl sulfate are added dropwise at room temperature while stirring to a solution of 19.99 parts mol) of (fi-dri n-butylamino ethyl) vinyl ether in 32.6 parts of methylene chloride. Operations are continued as described in Example 7, and there is obtained a clear colorless solution of about 48 percent strengthof the quaternary ammonium compound bf the formula which is suitable for polymerizations without further purification. 7

Example 10 A solution of 39.98 parts. of (fi-di-n-butylamino ethyl) vinyl ether in: 65.2 parts of methylene chloride is quaternatedwith 25.22 parts of dimethyl sulfate in the manner described in Example 9. For the purpose of polymerization, the solution of the monomeric quaternary ammonium compound is heated to 6570 C. and in the course of 8 hours 15.8 parts of a solution of 3 percent strength of borofluoride dihydrate in dioxane are added dropwise. The whole is finally polymerized for 2 hours at the same temperature. There are obtained 139 parts of a dark brown colored solution which has a resin content of 44.75 percent. The dark coloredresin free from solvent is soft and water-soluble. It can be' bleached by means of oxidation agents and is suitable as an adjuvant to sizing agents for the improvement of the electric conductivity of the film of the size.

In an analogous manner the quaternary ammonium compound from (-fl-moipholino ethyl) vinyl ether and dimethyl sulfate can' be polymerized; The resin free from solvent is a; wax-like dark colored mass.

Example 11 a V 37.5 parts of isobutyl' a'crylate and 10' parts of acrylonitrile are emulsified in a solution oh 1.62 parts of ['y- (lauroylamido)-propyl]-trimethyl ammonium; methosulfate in 57.5 parts of distilled water while stirring vigorously by mechanical means or agitating. To the emulsion are added? parts of the aqueous solution of 50 percent strength of the quaternary ammonium compound of the formula When spread on a' sub-' stratum and dried it forms a soft, rubber-like clear and can be mixed with selutio'ns of aluminium salt or cation-active softening agents without any signs of coagtv lation. The emulsion is absorbed substantively even from mixtures hi hly diluted with water on negatively charged textiles (for example wool), and is eminently suitable when mixed with paraflin emulsions containingaluminium salt for the production of water-fast dressings. Example 12 25.5 parts of acrylonitrile are mixed with 9 parts of an aqueous solution of 50 percent strength of the quaternary ammonium compound of the formula 04119 [CHFCH-0-CH,-CH -NGH ]OS0};CH;

prepared according to Example 8 and emulsified in a solution of 0.35 part of (2% calculated on the total quan tity of the monomers) IE(fi-lauroly-amido)'ethyl]-diethylmethyl-ammonium methosulfat'e in 67 parts of distilled water. Half of this emulsion is heated to 60 C. under nitrogen and While stirring, and to start the polymerization half of a solution of 0.05 part of potassium persulfate, 0.25 part of B-lauroylamido-ethyhdiethyl methyl ammonium methosulfate in 3 parts of distilled water is added. The other half of this catalyst solution is added to the remaining half of the aforementioned emulsion of monomers, and the latter is added dropwise in the course of 1 hour during polymerization. When this operation is complete, the Whole is heated for 1 /2 hours at 65 C. Then 0.1 part of potassium persulfate is added and the whole finally heated for 2 hours at -90 C. The precipitated fine-grained copolymer is filtered oil, washed With plenty of distilled Water and dried. It dissolves in dimethyl formamide and is suitable for the preparation of dyeable polyacrylonitrilc fibers or films.

Example 13 6 parts of acrylic acid amide are dissolved in 85 parts of distilled water and mixed with 8 parts of an aqueous solution of 50 percent strength of the monomeric quaternary ammonium compound from (B-di-nbutylamino)-ethyl]-vinyl ether anddimethylsulfate prepared according to Example 8. A

The whole is heated to 65 C. under nitrogen and with stirring, and in the course of 2 hours asolution of 0.1 part of potassium persulfate in 2 parts of distilled water is added in portions. The mixture is then stirred for an hour at 6570 C., after which polymerization is finished and a clear syrupy liquid is obtained. It has a polymer content of 9.95 percent and is suitable for the preparation of sizing agents which reduce the electrostatic charge of textiles or textile fibers.

Example 14 11.1 parts of the solution of 54 percent stiength of the quaternary ammonium salt from (fl -morpholino ethyl)-vinyl ether and dimethyl sulfate in methylene chloride described in Example 7 are mixed with 54 parts of methyl metha'erylate' and 83' parts of ethylene chloride and heated to 88 C. while stirring; 2 parts of a solution of- 10' percent strength of benzoyl peroxide in ethylene chloride are added gradually in the course of 3 /2 hours, and' the whole is then heated for 1 /2 hours at the same temperature. A- highly viscous weakly opalwith a resin content of 39.8 percent is obtained;

9 10 The solution of this copolymer is suitable especially 3. The quaternary ammonium compound of the in admixture with organic soluble urea or melamine formula formaldehyde gum-lac for the production of high quality stoving lacquers. 01

What is claimed is: I 3: Q1- 1. A new quaternary polymerizable vinyl ether which 44 CONE corresponds to the formula R1 9 4. The quaternary ammonium compound of the NR OCH=OH X 10 formula h R d' l 1 1 1 f th '1' E w erem 1s a ra ica se ec e rom e group consis mg of the gylcidyl radical and the carboxamido-methyl radi- {I cal; R and R form a member selected from the group 0 12-0 1 GHQ-430N112 consisting of 15 alkyl radmk References Cited in the file of this patent UNITED STATES PATENTS alkyl 2,368,208 Epstein Jan. 30, 1945 loweralkylefle k 2,581,285 Niederl et al. Jan. 1, 1952 2,649,444 Barrett Aug. 18, 1953 2654729 Price Oct. 6 1953 1 d1 1 4 and Walkylem 2,662,875 Chaney Dec. 15, 1953 lower alkylene radical 2,683,125 DAlelio July 6, 1954 2,686,173 Sauer Aug. 10, 1954 2,727,068 De Benneville Dec. 13, 1955 2,734,890 Bortnick et a1. Feb. 14, 1956 R is a lower alkylene radical in which two carbon atoms are linked to each other; and represents an anion. OTHER REFERENCES The quaternary ammomum compound of the Butler et al.: Journal of the American Chemical Soformula mm ciety, V01. 74, pp. 1939-41, April 20, 1952. 

1. A NEW QUATERNARY POLYMERIZABLE VINYL ETHER WHICH CORRESPONDS TO THE FORMULA
 4. THE QUATERNARY AMMONIUM COMPOUND OF THE FORMULA 